In this study, we experimentally and theoretically investigated the use of the symmetrical cyclic trifunctional initiator diethyl ketone triperoxide (DEKTP) in the bulk polymerization of styrene. The experimental study consisted of a series of isothermal batch polymerizations at different temperatures (120 and 130 C) with different initiator concentrations (0.005, 0.01, and 0.02 mol/L). A mathematical model was developed to predict the evolution of the reacting chemical species and the produced molecular weight distributions. The kinetic model included chemical and thermal initiation, propagation, transfer to the monomer, termination by combination, and reinitiation reactions. The simulation results predict the concentration of diradicals, monoradicals, and polymeric chains, characterized by the number of undecomposed peroxide groups. The experimental results showed that at reaction temperatures of 120-130 C, initiation by DEKTP produced an increase in the polymerization rates (R p 's) and average molecular weights, depending on the initiator concentration, due to sequential decomposition. The mathematical model was adjusted and validated with the experimental data. The theoretical predictions were in very good agreement with the experimental results. Also, an optimum initiator concentration was observed that achieved high R p 's and high molecular weights simultaneously. For polymerization temperatures of 120-130 C, the optimum concentration was 0.01 mol/L.
A mathematical model that simulates the curing process of benzoxazine (Bz) systems is presented. The model predicts the conversion, gel point and Tg along the curing process, and considers the diffusional limitations to mass transfer due to the increase in the system viscosity along the process. This model can be used to select an appropriate combination of time and temperature in order to obtain a material with pre-specified properties. The theoretical parameters were adjusted with experi-mental data: conversion, weight-average molecular weight, weight fraction of solubles and Tg. The Bz based on bisphenol A and aniline (BzBA) was used to adjust the model. The curing kinetic of this Bz was followed by FTIR, SEC and DSC, considering five different curing conditions. A very good agreement between experimental and simulated values was ob-served, even when curing is carried out under differ-ent temperatures profiles.
A detailed, comprehensive mathematical model for bulk polymerization of styrene using multifunctional initiators – both linear and cyclic – in a batch reactor was developed. The model is based on a kinetic mechanism that considers thermal initiation and chemical initiation by sequential decomposition of labile groups, propagation, transfer to monomer, termination by combination and re-initiation reactions due to undecomposed labile groups. The model predicts the evolution of global reaction variables (e.g, concentration of reagents, products, radical species and labile groups) as well as the evolution of the detailed complete polymer molecular weight distributions, with polymer species characterized by chain length and number of undecomposed labile groups. The mathematical model was adjusted and validated using experimental data for various peroxide-type multifunctional initiators: diethyl ketone triperoxide (DEKTP, cyclic trifunctional), pinacolone diperoxide (PDP, cyclic bifunctional) and 1,1-bis(tert-butylperoxy)cyclohexane (L331, linear bifunctional). The model very adequately predicts polymerization rates and complete molecular weight distributions. The model is used to theoretically evaluate the influence of initiator structure and functionality as well as reaction conditions.
This work experimentally and theoretically investigates the use of the symmetrical cyclic trifunctional initiator diethyl ketone triperoxide (DEKTP) in the bulk polymerization of styrene (St). The study focused on temperatures of 150 to 200 C, considering chemical initiation by both sequential and total decomposition reactions. The experimental work consisted of a series of isothermal batch polymerizations at higher temperatures, 150 and 200 C, with an initiator concentration of 0.01 mol/L. The mathematical model is based on a kinetic mechanism that includes thermal and chemical initiation (both sequential and total decomposition reactions), propagation, transfer to monomer, termination by combination and re-initiation reactions. Experimental and theoretical results show that the decomposition mechanism of the initiator is modified by the reaction temperature and can be modeled as a set of two parallel reactions with different temperature dependences. The developed mathematical model simulates the bulk polymerization of St in the presence of DEKTP for a wide temperature range (120-200 C). It was found that due to these two decomposition mechanisms, the system may behave as a "dead-end" polymerization system above a certain temperature, yielding low molecular weights and a limiting conversion value. Simulation results indicate the value of this temperature to be about 185 C. POLYM. ENG. SCI., 55:145-155, 2015.
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